Fluoride in thermal and non-thermal groundwater: Insights from geochemical modeling.

High fluoride (F) groundwaters (>1 mg/L) have been recognized as a water quality problem for nearly a century and occur in many countries worldwide. The affected aquifers can be sedimentary, metamorphic or igneous rocks, but the process giving rise to high-F concentrations has been studied with geochemical modeling and an examination of the rock sources. The association of high-F with silicic igneous rocks such as granites and rhyolites results from magmatic differentiation (fractional crystallization, fractional melting, and crustal assimilation) wherein F is enriched in the liquid phase because of its incompatibility in the mafic minerals that crystallize early during cooling. Further development of F-rich groundwaters occurs during the evolution of Na-HCO3 waters because of removal of Ca through ion-exchange and calcite precipitation, thereby raising the F concentration from minerals like fluorite and fluorapatite to maintain solubility equilibrium. Increasing temperatures enhance this effect because of the retrograde solubility of calcite. From geochemical modeling using the PhreeqcI code, the primary variables controlling F concentrations are DIC (dissolved inorganic carbon), salinity (ionic strength), PCO2, and temperature. Complexing is also important but plays a more secondary role. Considering these variables, an improved set of plotting parameters, F/Cl vs. HCO3/Cl, are shown to be effective in interpreting groundwater analyses. This approach is demonstrated by examining case studies from the Black Creek aquifer, South Carolina, USA, the Madison regional aquifer, midwestern USA, the Mizunami Underground Research Laboratory, Japan, New Zealand thermal waters, the San Luis Valley groundwaters, Colorado, USA, and the Aquia aquifer, Maryland, USA.

Origin and geochemistry of arsenic in surface and groundwaters of Los Pozuelos basin, Puna region, Central Andes, Argentina.

Los Pozuelos is a closed basin in the Puna region of NW Argentina, Central Andes. This is a semi-arid region where closed basins are the most important feature for the hydrologic systems. The center of the basin is occupied by a fluctuating playa lake called Los Pozuelos lagoon, which constitutes a UNESCO Biosphere Reserve. This is one of the most populated closed basins in the Argentinian Puna and residents use groundwater for drinking and cooking. Lowest concentrations of As and dissolved solids are in the headwaters of the rivers (1.46-27 µg/L) and the highest concentrations are in the lagoon (43.7-200.3 µg/L). In groundwater, arsenic concentrations increase from the outer ring aquifer (3.82-29.7 µg/L) composed of alluvial-alluvial fan sediments to the inner lacustrine aquifer (10-113 µg/L) that surround the playa lake. Moreover, high concentrations of As during the dry season (90.2 and 113 µg/L), Na/K mass ratios (0.2 and 0.3), and formation of Na-rich efflorescent salts suggest that high evaporation rates increases As concentration, while rainwater dilutes the concentration during the wet season. As(V) is the dominant species in all the water types, except for the lagoon, where As(III) occasionally dominates because of organic matter buildup. There are at least three potential sources for As in water i) oxidation of As sulfides in Pan de Azúcar mine wastes, and acid mine drainage discharging into the basin; ii) weathering and erosion of mineralized shales; iii) weathering of volcanic eruptive non-mineralized rocks. Because it is a closed basin, the arsenic released from the natural and anthropogenic sources is transported in solution and in fluvial sediments and finally accumulates in the center of the basin where the concentration in water increases by evaporation with occasional enhancement by organic matter interaction in the lagoon.

Sulfolobus islandicus meta-populations in Yellowstone National Park hot springs.

Abiotic and biotic forces shape the structure and evolution of microbial populations. We investigated forces that shape the spatial and temporal population structure of Sulfolobus islandicus by comparing geochemical and molecular analysis from seven hot springs in five regions sampled over 3 years in Yellowstone National Park. Through deep amplicon sequencing, we uncovered 148 unique alleles at two loci whose relative frequency provides clear evidence for independent populations in different hot springs. Although geography controls regional geochemical composition and population differentiation, temporal changes in population were not explained by corresponding variation in geochemistry. The data suggest that the influence of extinction, bottleneck events and/or selective sweeps within a spring and low migration between springs shape these populations. We suggest that hydrologic events such as storm events and surface snowmelt runoff destabilize smaller hot spring environments with smaller populations and result in high variation in the S. islandicus population over time. Therefore, physical abiotic features such as hot spring size and position in the landscape are important factors shaping the stability and diversity of the S. islandicus meta-population within Yellowstone National Park.

MDI Biological Laboratory Arsenic Summit: Approaches to Limiting Human Exposure to Arsenic.

This report is the outcome of the meeting "Environmental and Human Health Consequences of Arsenic" held at the MDI Biological Laboratory in Salisbury Cove, Maine, August 13-15, 2014. Human exposure to arsenic represents a significant health problem worldwide that requires immediate attention according to the World Health Organization (WHO). One billion people are exposed to arsenic in food, and more than 200 million people ingest arsenic via drinking water at concentrations greater than international standards. Although the US Environmental Protection Agency (EPA) has set a limit of 10 µg/L in public water supplies and the WHO has recommended an upper limit of 10 µg/L, recent studies indicate that these limits are not protective enough. In addition, there are currently few standards for arsenic in food. Those who participated in the Summit support citizens, scientists, policymakers, industry, and educators at the local, state, national, and international levels to (1) establish science-based evidence for setting standards at the local, state, national, and global levels for arsenic in water and food; (2) work with government agencies to set regulations for arsenic in water and food, to establish and strengthen non-regulatory programs, and to strengthen collaboration among government agencies, NGOs, academia, the private sector, industry, and others; (3) develop novel and cost-effective technologies for identification and reduction of exposure to arsenic in water; (4) develop novel and cost-effective approaches to reduce arsenic exposure in juice, rice, and other relevant foods; and (5) develop an Arsenic Education Plan to guide the development of science curricula as well as community outreach and education programs that serve to inform students and consumers about arsenic exposure and engage them in well water testing and development of remediation strategies.

Microbial oxidation of arsenite in a subarctic environment: diversity of arsenite oxidase genes and identification of a psychrotolerant arsenite oxidiser.

BACKGROUND: Arsenic is toxic to most living cells. The two soluble inorganic forms of arsenic are arsenite (+3) and arsenate (+5), with arsenite the more toxic. Prokaryotic metabolism of arsenic has been reported in both thermal and moderate environments and has been shown to be involved in the redox cycling of arsenic. No arsenic metabolism (either dissimilatory arsenate reduction or arsenite oxidation) has ever been reported in cold environments (i.e. < 10 degrees C). RESULTS: Our study site is located 512 kilometres south of the Arctic Circle in the Northwest Territories, Canada in an inactive gold mine which contains mine waste water in excess of 50 mM arsenic. Several thousand tonnes of arsenic trioxide dust are stored in underground chambers and microbial biofilms grow on the chamber walls below seepage points rich in arsenite-containing solutions. We compared the arsenite oxidisers in two subsamples (which differed in arsenite concentration) collected from one biofilm. 'Species' (sequence) richness did not differ between subsamples, but the relative importance of the three identifiable clades did. An arsenite-oxidising bacterium (designated GM1) was isolated, and was shown to oxidise arsenite in the early exponential growth phase and to grow at a broad range of temperatures (4-25 degrees C). Its arsenite oxidase was constitutively expressed and functioned over a broad temperature range. CONCLUSIONS: The diversity of arsenite oxidisers does not significantly differ from two subsamples of a microbial biofilm that vary in arsenite concentrations. GM1 is the first psychrotolerant arsenite oxidiser to be isolated with the ability to grow below 10 degrees C. This ability to grow at low temperatures could be harnessed for arsenic bioremediation in moderate to cold climates.

Ecological distribution and population physiology defined by proteomics in a natural microbial community.

An important challenge in microbial ecology is developing methods that simultaneously examine the physiology of organisms at the molecular level and their ecosystem level interactions in complex natural systems. We integrated extensive proteomic, geochemical, and biological information from 28 microbial communities collected from an acid mine drainage environment and representing a range of biofilm development stages and geochemical conditions to evaluate how the physiologies of the dominant and less abundant organisms change along environmental gradients. The initial colonist dominates across all environments, but its proteome changes between two stable states as communities diversify, implying that interspecies interactions affect this organism's metabolism. Its overall physiology is robust to abiotic environmental factors, but strong correlations exist between these factors and certain subsets of proteins, possibly accounting for its wide environmental distribution. Lower abundance populations are patchier in their distribution, and proteomic data indicate that their environmental niches may be constrained by specific sets of abiotic environmental factors. This research establishes an effective strategy to investigate ecological relationships between microbial physiology and the environment for whole communities in situ.

Methylmercury enters an aquatic food web through acidophilic microbial mats in Yellowstone National Park, Wyoming.

Microbial mats are a visible and abundant life form inhabiting the extreme environments in Yellowstone National Park (YNP), WY, USA. Little is known of their role in food webs that exist in the Park's geothermal habitats. Eukaryotic green algae associated with a phototrophic green/purple Zygogonium microbial mat community that inhabits low-temperature regions of acidic (pH approximately 3.0) thermal springs were found to serve as a food source for stratiomyid (Diptera: Stratiomyidae) larvae. Mercury in spring source water was taken up and concentrated by the mat biomass. Monomethylmercury compounds (MeHg(+)), while undetectable or near the detection limit (0.025 ng l(-1)) in the source water of the springs, was present at concentrations of 4-7 ng g(-1) dry weight of mat biomass. Detection of MeHg(+) in tracheal tissue of larvae grazing the mat suggests that MeHg(+) enters this geothermal food web through the phototrophic microbial mat community. The concentration of MeHg(+) was two to five times higher in larval tissue than mat biomass indicating MeHg(+) biomagnification occurred between primary producer and primary consumer trophic levels. The Zygogonium mat community and stratiomyid larvae may also play a role in the transfer of MeHg(+) to species in the food web whose range extends beyond a particular geothermal feature of YNP.

Thioarsenates in geothermal waters of Yellowstone National Park: determination, preservation, and geochemical importance.

Mono-, di-, tri-, and tetrathioarsenate, as well as methylated arsenic oxy- and thioanions, were determined besides arsenite and arsenate in geothermal waters of Yellowstone National Park using anion-exchange chromatography inductively coupled plasma mass spectrometry. Retention time match with synthetic standards, measured S:As ratios, and molecular electrospray mass spectra support the identification. Acidification was unsuitable for arsenic species preservation in sulfidic waters, with HCI addition causing loss of total dissolved arsenic, presumably by precipitation of arsenic-sulfides. Flash-freezing is preferred for the preservation of arsenic species for several weeks. After thawing, samples must be analyzed immediately. Thioarsenates occurred over a pH range of 2.1 to 9.3 in the geothermal waters. They clearly predominated under alkaline conditions (up to 83% of total arsenic), but monothioarsenate also was detected in acidic waters (up to 34%). Kinetic studies along a drainage channel showed the importance of thioarsenates for the fate of arsenic discharged from the sulfidic hot spring. The observed arsenic speciation changes suggest three separate reactions: the transformation of trithioarsenate to arsenite (major initial reaction), the stepwise ligand exchange from tri- via di- and monothioarsenate to arsenate (minor reaction), and the oxidation of arsenite to arsenate, which only becomes quantitatively important after thioarsenates have disappeared.

Aqueous stability of gadolinium in surface waters receiving sewage treatment plant effluent, Boulder Creek, Colorado.

In many surface waters, sewage treatment plant (STP) effluent is a substantial source of both regulated and unregulated contaminants, including a suite of complex organic compounds derived from household chemicals, pharmaceuticals, and industrial and medical byproducts. In addition, STP effluents in some urban areas have also been shown to have a positive gadolinium (Gd) anomaly in the rare earth element (REE) pattern, with the Gd derived from its use in medical facilities. REE concentrations are relatively easy to measure compared to many organic wastewater compounds and may provide a more widely utilized tracer of STP effluents. To evaluate whether sewage treatment plant-associated Gd is a useful tracer of treatment plant effluent, an investigation of the occurrence, fate, and transport of rare earth elements was undertaken. The rare earth element patterns of four of five STP effluents sampled display positive Gd anomalies. The one site that did not have a Gd anomaly serves a small community, population 1200, with no medical facilities. Biosolids from a large metropolitan STP are not enriched in Gd even though the effluent is, suggesting that a substantial fraction of Gd remains in the aqueous phase through routine treatment plant operation. To evaluate whether STP-derived Gd persists in the fluvial environment, a 14-km study reach downstream of an STP was sampled. Gadolinium anomalies were present at all five downstream sites, but the magnitude of the anomaly decreased. Effluent from STPs is a complex mixture of organic and inorganic constituents, and to better understand the chemical interactions and their effect on REEs, the aqueous speciation was modeled using comprehensive chemical analyses of water samples collected downstream of STP input. These calculations suggest that the REEs will likely remain dissolved because phosphate and carbonate complexes dominate over free REE ions. This study supports the application of Gd anomalies as a useful tracer of urban wastewater.

Sulfur geochemistry of hydrothermal waters in Yellowstone National Park, Wyoming, USA. III. An anion-exchange resin technique for sampling and preservation of sulfoxyanions in natural waters.

A sampling protocol for the retention, extraction, and analysis of sulfoxyanions in hydrothermal waters has been developed in the laboratory and tested at Yellowstone National Park and Green Lake, NY. Initial laboratory testing of the anion-exchange resin Bio-Rad™ AG1-X8 indicated that the resin was well suited for the sampling, preservation, and extraction of sulfate and thiosulfate. Synthetic solutions containing sulfate and thiosulfate were passed through AG1-X8 resin columns and eluted with 1 and 3 M KCl, respectively. Recovery ranged from 89 to 100%. Comparison of results for water samples collected from five pools in Yellowstone National Park between on-site 1C analysis (U.S. Geological Survey mobile lab) and IC analysis of resin-stored sample at SUNY-Stony Brook indicates 96 to 100% agreement for three pools (Cinder, Cistern, and an unnamed pool near Cistern) and 76 and 63% agreement for two pools (Sulfur Dust and Frying Pan). Attempts to extract polythionates from the AG1-X8 resin were made using HCl solutions, but were unsuccessful. Bio-Rad™ AG2-X8, an anion-exchange resin with weaker binding sites than the AG1-X8 resin, is better suited for polythionate extraction. Sulfate and thiosulfate extraction with this resin has been accomplished with KCl solutions of 0.1 and 0.5 M, respectively. Trithionate and tetrathionate can be extracted with 4 M KCl. Higher polythionates can be extracted with 9 M hydrochloric acid. Polythionate concentrations can then be determined directly using ion chromatographic methods, and laboratory results indicate recovery of up to 90% for synthetic polythionate solutions using AG2-X8 resin columns.